Lecture ONE - Stoichiometry

Third Stage
Subject: Chemical Reaction Kinetics

Lecture- ONE
Prof . Dr. Mohammad Fadhil
Al-Turath University
1
L P T C
2 - 1 2
Ref. Books:
 Chemical Reaction Engineering – Octave Leven
Spiel, 3rd Edition, John Wiley & Sons
 G.F. Froment and K.B. Bischoff, Chemical Reactor

Analysis and Design, 3rd Edition, John Wiley & Sons
2
Types of Reactors
(a)
(b)
3
Comparison of batch and continuous operation
(advantage, and disadvantage)
4
Stoichiometry
4NH3 + 5O2  6H2O + 4NO
Can mean either:
4 molecules of NH3 react with 5 molecules of O2
to produce 6 molecules of H2O and 4 molecules of NO
OR
4 moles of NH3 react with 5 moles of O2
to produce 6 moles of H2O and 4 mol
5
Limiting Reactant: (for irreversible reaction)
The limiting reactant is the reactant present in the smallest
stoichiometric amount A + B C
Excess Reactant: The excess reactant is the reactant which
is not completely consumed in the reaction
Equilibrium: (for reversible reaction)

A reversible reaction reaches equilibrium when no further changes
take place in the concentration of the reactants and products.
At equilibrium:
the rate of the forward reaction is equal to the rate of the
reverse reaction. A + B C
Conversion of a reactant
Reactant A
time
7
• The theoretical Product yield: is the maximum
amount of product that can be produced from a
given amount of reactant with a complete
reaction.
• The actual Product yield: of a product is the

measured amount of that product obtained from
a non-complete reaction.
• The percentage Product yield: is the ratio of the

actual yield to the theoretical yield, multiplied by
100.
actual yield
percentage yield   100
theorectical yield
8
Yield & Selectivity of Multiple reactions
CH4 + O2  HCHO (desired product) + H20
CH4 + 2O2  CO2 + 2H20
The yield of a multiple reaction is the ratio of the desired
product formed (in moles) to the moles of reactant
consumed.
The selectivity of a multiple reaction is the ratio of the
desired product formed (in moles) to the moles of
undesired product formed.
9
Example1: Ethane Combustion
10
Chemical Kinetics:
Studies the rate at which a chemical process occurs.
Besides information about the speed at which reactions
occur, kinetics also sheds light on the reaction mechanism
(exactly how the reaction occurs).
Reaction Rates How we measure rates.
How the rate depends on

Rate Laws amounts of reactants.
How to calc amount left or time to
Integrated Rate Laws reach a given amount.
How long it takes to react 50% of
Half-life reactants.
How rate constant changes with
Arrhenius Equation T.
Link between rate and molecular
Mechanisms scale processes. 11
Chemical reaction rate
Reaction rate is the change in the concentration of a
reactant or a product with time (mole / L. s).
A B
change in concentration of A conc A 2  conc A1 Δ  A 

Rate   
change in time t2  t1 Δt
D[A]
rate = - D[A] = change in concentration of A over
Dt
time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
12
Reaction Rates and Stoichiometry
If we have the reaction,

aA + bB cC + dD
Reactants (decrease) Products (increase)
𝟏 𝟏 𝟏 𝟏
𝒓𝑨 = 𝒓𝑩 = 𝒓𝑪 = 𝒓𝑫
𝒂 𝒃 𝒄 𝒅
13
Parameters which Influence Reaction
Rates
 Concentration of Reactants
As the concentration of reactants increases, so does the
likelihood that reactant molecules will collide.
 Temperature
At higher temperatures, reactant molecules have more
kinetic energy, move faster, and collide more often and with
greater energy.
 Catalysts
Speed reaction by changing mechanism.
14
Collision theory
 Molecules must collide to react.
 Concentration affects rates because collisions are more likely.
 Must collide hard enough.
 Number of collisions with the required energy = z e- Ea /RT , z :
collision number
 Temperature increases the number of collisions.
Activation energy (Ea):
Activation energy (Ea): "the minimum amount of energy (in kJ/mole)
that must be absorbed by a system to initiate it to react"
Exothermic endothermic 15
Reaction Rate Law for Irreversible
Reaction
aA + bB cC + dD
Rate α [A]m [B]n
Rate = k [A]m [B]n

k : rate constant = f(T)
Reactions order = m+ n
For Elementry Reaction:
m = a and n = b
Rate = k [A]a [B]b

16
For the reaction:
A B
17
Relationships between rate, rate constant, activation
energy, & temperature.
The temperature dependency of k is described by the Arrhenius
equation:
k  Ae Ea / RT ;
Ea  1
Straight line from: ln k  ln A   
R T
where,
A = pre-exponential or frequency factor
Ea = activation energy [J/mol; cal/mol]
R = gas constant = 8.314 J/mol·K = 1.987 cal/mol·K
T = absolute temperature [K]
* If data is available at two different temperatures (T1 & T2):

k2 Ea  1 1 
ln    
k1 R  T2 T1 
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Tutorial
1- In the reaction A B
the relation between reaction rate constant ( k )and
temperature (T) of reactant A is listed in the following table.
(a) Calculate the activation energy.
(b) Arrhenius pre-exponential factor for this reaction.
Temperature ℃ k （s-1）
22.2 7.0×10-4
27.2 5.5×10-4
33.7 9.1×10-3
38.0 8.4×10-3
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Answer
T (0C) T (K) 1/T (K-1) k (s-1) ln k
22.2 295.2 0.00338 7.0×10-4 -7.7836
27.2 300.2 0.00333 5.5×10-4 -6.8189
33.7 306.7 0.00326 9.1×10-3 - 6.5916
38.0 311 0.00321 8.4×10-3 - 6.3847
Draw a plot of ln (k) versus 1/T
From plot:
ln A= -6.2
A = e-6.2 = 2 x 10-3
𝐸
Slope = − 𝑎 = - 8229
𝑅
𝐸𝑎 = 8.314 𝑥 8229 = 68416 𝐽/𝑚𝑜𝑙
20
2- Compound A is decomposed totally in 30 min when heated to 63OC. At
74°C the compound is totally decomposed in 15 sec. Calculate the
activation energy (Ea) for the decomposition reaction of compound A.
Answer
t1 = 30 min at TI = 63 + 273 = 336 K

t2 = 15 sec at T2 = 74 + 273 = 347 K
From the data, the reaction rate is proportional to temperature but

inversely proportional to reaction time.
E = 422000 J/mol
21
3- Hydrogen gas is combusted with Oxygen according to the
reaction:
H2 (g) + O2 (g) 2H2O(g)
(a) Write the rate in terms of varying [H2], [O2], and [H2O]
with time.
(b) At how much rate will [H2O] increasing? When [O2] is
decreasing at 0.23 mol/L⋅s
Answer
(a)
Δ O2  1 Δ  H 2  1 Δ  H 2O 
Rate    
Δt 2 Δt 2 Δt
(b)
1 Δ  H 2O Δ  O2   mol 
    0.23 
2 Δt Δt  Ls
Δ  H 2O  mol  mol
 2  0.23   0.46
Δt  Ls  Ls
22
4- For the reaction :
2 NO2(g)  2 NO(g) + O2(g)
the primary concentration of NO2 was 1x 10-2 mol/L and its concentration after
150 s was 55x 10-4 mol/L.
(a) During the first 150 s, calculate the average rates of this reaction during the
first 150 s.
(b) Also calculate the average rate during the second 150 s.
Answer
- D[NO 2 ]
Average rate =
Dt
- (0.0055 mol/L - 0.0100 mol/L)
=
150 s
0.0045 mol/L
=
150 s
= 3.0 x 10-5 mol/(L.s)
23
(b) During the second 150 s
- D[NO 2 ]
Average rate =
Dt
- (0.0038 mol/L - 0.0055 mol/L)
=
150 s
0.0017 mol/L
=
150 s
= 1.1 x 10-5 mol/(L.s)
Because the reactant concentration has decreased , the

average rate decreases as reaction progresses
24

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Third Stage

Subject: Chemical Reaction Kinetics

 G.F. Froment and K.B. Bischoff, Chemical Reactor

Equilibrium: (for reversible reaction)

• The actual Product yield: of a product is the

• The percentage Product yield: is the ratio of the

How the rate depends on

change in concentration of A conc A 2  conc A1 Δ  A 

If we have the reaction,

Reactants (decrease) Products (increase)

Rate = k [A]m [B]n

For Elementry Reaction:

Rate = k [A]a [B]b

* If data is available at two different temperatures (T1 & T2):

Draw a plot of ln (k) versus 1/T

t1 = 30 min at TI = 63 + 273 = 336 K

From the data, the reaction rate is proportional to temperature but

= 1.1 x 10-5 mol/(L.s)

Because the reactant concentration has decreased , the

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